CN106916093B - A kind of method that N-heterocyclic carbine catalyzes and synthesizes polysubstituted pyrrole alkane ketone compounds - Google Patents
A kind of method that N-heterocyclic carbine catalyzes and synthesizes polysubstituted pyrrole alkane ketone compounds Download PDFInfo
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Abstract
The invention belongs to synthetic organic chemical arts, and in particular to a kind of method that N-heterocyclic carbine catalyzes and synthesizes polysubstituted pyrrole alkane ketone compounds.The present invention is using alkene aldehyde compound and α-aminoacidesters as raw material, under the action of organic solvent, alkali and oxidant, under room temperature environment, using N-heterocyclic carbine as catalyst, pyrrolidones are made after reaction, products therefrom is isolated and purified by recrystallization or thin-layer chromatography or column chromatography.Preparation method green high-efficient of the present invention, compared with the conventional method, this method can fit that substrate spectrum is wide, and substrate is conveniently easy to get, and reaction condition is mild, easy to operate, and reaction efficiency is high.
Description
Technical field
The invention belongs to synthetic organic chemical arts, and in particular to a kind of N-heterocyclic carbine catalyzes and synthesizes polysubstituted pyrrole alkane
The method of ketone compounds.
Background technique
Pyrrolidones have in biological medicine and study on the synthesis as a kind of important organic compound
Highly important effect (Williams, P. G.; Buchanan, G. O.; Feling, R. H.; Kauffman, C.
A.; Jensen, P. R.; Fenical, W. J. Org. Chem.2005, 70, 6196).Currently, pyrrolidinone compounds
The representative synthetic schemes for closing the synthesis of object has the condensation of amine and carboxylic acid derivates；The oxyradical of open chain compound is cyclized；
Cycloaddition ((a) Vellalath, S. of metal catalytic; Van, K. N.; Romo, D.Angew. Chem. Int. Ed. 2013, 52, 13688. (b) Liu, Q.; Ferreira, E. M.; Stoltz, B. M. J. Org. Chem. 2007, 72, 7352. (c) Yoshioka, S.; Nagatomo, M.; Inoue, M. Org. Lett.2015, 17, 90).But these methods have certain limitation, if raw material needs pre- function dough, react item
Part is relative complex harsh (high temperature, expensive catalyst etc.), has by-product (Atom economy is not high), limited substrate spectrum with
And in terms of Green Chemistry, so limiting its application in big quantitative response or industrial production.It is honest and clean thus to develop a kind of raw material
Valence is easy to get, step is simple and convenient to operate, mild condition, wide application range of substrates and high-efficient synthesis polysubstituted pyrrole alkane
The method of ketone compounds is key points and difficulties.The present inventor development be with alkene aldehyde compound, a-amino acid ester compounds
Raw material is used as catalyst with N-heterocyclic carbine (N-Heterocyclic Carbene, NHC), in the presence of oxidant, uses
Suitable alkali synthesis polysubstituted pyrrole alkane ketone compounds method is a kind of simple and practical synthetic method.
Summary of the invention
The invention aims to provide a kind of method for being efficiently synthesized polysubstituted pyrrole alkane ketone compounds.This method is
Using alkene aldehyde compound, a-amino acid ester compounds as raw material, in the presence of oxidant, using N-heterocyclic carbine as catalysis
Agent reacts certain time at room temperature and polysubstituted pyrrole alkane ketone compounds is made.
Pyrrolidones of the invention are the presence of alkali and at room temperature in organic solvent, with olefine aldehydr class chemical combination
Object, a-amino acid ester compounds are that raw material, using N-heterocyclic carbine as catalyst, reacts at room temperature under the action of oxidant
Polysubstituted pyrrole alkane ketone compounds are made in certain time.
It can be represented by the formula:
The general molecular formula of the alkene aldehyde compound is:；The general molecular formula of a-amino acid ester compounds
It is:；The general molecular formula of synthesized pyrrolidones is:.In formula: R is alkyl,
Substituted ethylene base, polysubstituted phenyl, thiazole, furans, one of pyridine, in addition a variety of substituted-phenyls being previously mentioned are unless say
It is bright, usually mono-substituted o-, m-, in contraposition electrophilic and electron donating group, further preferred polysubstituted electrophilic and
Electron donating group, especially polysubstituted electron-withdrawing group；R1For in sulfonyl, acetyl group, benzoyl, alkyl, aryl
One kind, preferably sulfonyl；R2For alkyl or substituted aryl；R3For alkyl, substituted aryl, acyl group or alkoxy carbonyl group；R4, R5For alkane
Base or substituted aryl.The alkyl being previously mentioned refers generally to methyl, ethyl and benzyl, further preferred isopropyl unless otherwise stated
Or the biggish substituent group of tert-butyl, especially steric hindrance；
The N-heterocyclic carbine (NHC) is one of imidazoles, triazole, thiazoles salt；
The oxidant is one of benzoquinones, manganese dioxide, high-valency metal salt, air；
The alkali is the common inorganic bases and three such as potassium carbonate, sodium carbonate, potassium phosphate, potassium acetate, sodium alkoxide, sodium hydroxide
One of common organic bases such as ethamine, 11 carbon -7- alkene of 1,8- diazabicylo；
The alkene aldehyde compound, α-aminoacidesters molar ratio are 1: 1 ~ 1: 3；
The molar ratio of the alkene aldehyde compound and oxidant is 1: 1 ~ 1: 3；
The molar ratio of the alkene aldehyde compound and N-heterocyclic carbine is 1: 0.1 ~ 1: 0.2；
The molar ratio of the alkene aldehyde compound and alkali is 1: 1 ~ 1: 4；
Reaction temperature is room temperature；
The organic solvent is acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, ether, methylene chloride, three
One of chloromethanes or toluene, preferably acetonitrile or methylene chloride.
The present invention prepares products therefrom and is separated by the methods of recrystallization or thin-layer chromatography or column chromatography.Such as with tying again
Brilliant method, recommending solvent is the mixed solvent of polar solvent and nonpolar solvent, recommend solvent can for methylene chloride-just oneself
Alkane, isopropanol-petroleum ether, ethyl acetate-petroleum ether, ethyl acetate-n-hexane or isopropanol-ethyl acetate-petroleum ether
Equal mixed solvents.With thin-layer chromatography and column chromatography method, solvent used is that the mixing of polar solvent and nonpolar solvent is molten
Agent, recommending solvent can be isopropanol-petroleum ether, ethyl acetate-petroleum ether, ethyl acetate-n-hexane or isopropanol-acetic acid
The mixed solvents such as ethyl ester-petroleum ether, volume ratio can be respectively: polar solvent: nonpolar solvent=1: 3 ~ 1:
10.Such as: ethyl acetate: petroleum ether=1: 3 ~ 1: 10, isopropanol: petroleum ether=1: 3 ~ 1: 10.
Beneficial effects of the present invention:
What it is the present invention provides a kind of green high-efficient is raw material by alkene aldehyde compound, α-aminoacidesters, is deposited in oxidant
Under, using N-heterocyclic carbine as catalyst, the method for high efficiency one-step synthesis pyrrolidones.With existing method phase
Than this method is applicable to a variety of different types of alkene aldehyde compounds, and reaction condition is mild, and raw material is cheap and easy to get, operation letter
Just, the yield of reaction is also preferable, has Atom economy, also embodies the theory of Green Chemistry well.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of 1 product of embodiment.
Fig. 2 is the carbon-13 nmr spectra of 1 product of embodiment.
Fig. 3 is the nuclear magnetic resonance spectroscopy of 2 product of embodiment.
Fig. 4 is the carbon-13 nmr spectra of 2 product of embodiment.
Fig. 5 is the nuclear magnetic resonance spectroscopy of 3 product of embodiment.
Fig. 6 is the carbon-13 nmr spectra of 3 product of embodiment.
Specific embodiment
It will be helpful to understand the present invention by following embodiments, but be not intended to limit the contents of the present invention.
Embodiment 1
Under nitrogen protection, α-aminoacidesters (0.05 mmol), NHC (0.01 are sequentially added into a dry reaction pipe
mmol), K2CO3 (0.1 mmol), oxidant (0.075 mmol), olefine aldehydr (0.075 mmol) are then added 5 into system
mL CH3CN, reacting 12 h at room temperature terminates, and stops stirring.Column chromatography, eluent: ethyl acetate and petroleum ether are with volume ratio 1:
3 mixing, collect component, and obtaining corresponding product is yellow solid, yield 75%.The title of product are as follows: 5- oxo -3- phenyl -1- toluene
Sulfonyl-pyrrolidine -2,2- diethyl dicarboxylate.Structural formula is as follows:
The fusing point of the product Compound is as follows: Mp 137-140 °C；The hydrogen nuclear magnetic resonance modal data of compound is as follows:1H
NMR (400 MHz,CDCl3) δ 8.07 (d, J = 8.0 Hz, 2H), 7.35-7.22 (m, 5H), 7.12 (d, J
= 8.0 Hz, 2H), 4.43 (q, J = 7.1 Hz, 2H), 4.07 (t, J = 8.3 Hz, 1H), 3.97-3.89
(m, 1H), 3.84-3.79 (m, 1H), 2.95-2.79 (m, 2H), 2.45 (s, 3H), 1.39 (t, J = 7.1
Hz, 3H), 0.96 (t, J= 7.1 Hz, 3H);The carbon-13 nmr spectra data of compound are as follows:13C NMR (100
MHz, CDCl3) δ 172.0, 167.1, 165.0, 145.2, 135.4, 135.3, 129.9, 128.9, 128.5,
128.4, 128.3, 63.1, 62.5, 46.7, 36.2, 21.7, 13.8, 13.3;The Low Resolution Mass Spectra number of compound
According to as follows: MS (ESI) calcd for C23H26NO7S (M+H)+: 460.1, found: 460.2;The high score of compound
Distinguish that mass spectrometric data is as follows: HRMS (ESI) calcd for C23H26NO7S (M+H)+: 460.1425, found
460.1431。
Embodiment 2
Under nitrogen protection, α-aminoacidesters (0.5 mmol), NHC (0.075 are sequentially added into a dry reaction pipe
mmol), K2CO3 Methyl cinnamic aldehyde (1 mmol) is then added in (0.75 mmol), oxidant (1 mmol) into system
50 mL CH3CN, reacting 12 h at room temperature terminates, and stops stirring.Column chromatography, eluent: ethyl acetate and petroleum ether are with volume
It is mixed than 1:3, collects component, obtaining corresponding product is white solid, yield 82%.The title of product are as follows: 5- oxo -3-(is to toluene
Base) -1- tosyl pyrrolidines -2,2- diethyl dicarboxylate.Structural formula is as follows:
The fusing point of the product Compound is as follows: Mp 128-130 °C;The hydrogen nuclear magnetic resonance modal data of compound is as follows:1H
NMR (400 MHz, CDCl3) δ 8.07 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H),
7.10 (d, J = 7.9 Hz, 2H), 6.99 (d, J = 8.0 Hz, 2H), 4.46-4.38 (m, 2H), 4.05-
3.91 (m, 2H), 3.87-3.79 (m, 1H), 2.92-2.80 (m, 2H), 2.44 (s, 3H), 2.31 (s,
3H), 1.39 (t, J = 7.1 Hz, 3H), 0.99 (t, J= 7.1 Hz, 3H);The carbon-13 nmr spectra of compound
Data are as follows:13C NMR (100 MHz, CDCl3) δ 172.2, 167.1, 165.0, 145.1, 138.4, 135.4,
132.2, 129.9, 129.1, 128.9, 128.2, 77.4, 63.1, 62.4, 46.6, 36.3, 21.7, 21.0,
13.9, 13.4;The Low Resolution Mass Spectra data of compound are as follows: MS (ESI) calcd for C24H28NO7S (M+H)+:
474.2, found: 474.2;The high resolution mass spectrum data of compound is as follows: HRMS (ESI) calcd for C24H28NO7S
(M+H)+: 474.1581, found 474.1590。
Embodiment 3
Under nitrogen protection, α-aminoacidesters (0.2 mmol), NHC (0.02 are sequentially added into a dry reaction pipe
mmol), Et325 mL CH are then added to chlorocinnamaldehyde (0.2 mmol) in N (0.6 mmol) into system2Cl2, in sky
Reacting 15 h in gas at room temperature terminates, and stops stirring.Solvent is evaporated, using CH2Cl2With n-hexane recrystallize corresponding product is
White solid, yield 81%.The title of product are as follows: 3-(4- chlorphenyl) -5- oxo -1- tosyl pyrrolidines -2,2- dicarboxyl
Diethyl phthalate.Structural formula is as follows:
The melting point data of the product Compound is as follows: Mp 173-176 °C;The hydrogen nuclear magnetic resonance modal data of compound is such as
Under:1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.3 Hz,
2H), 7.28 (d, J = 8.3 Hz, 2H), 7.06 (d, J = 8.5 Hz, 2H), 4.48-4.37 (m, 2H),
4.08-3.95 (m, 2H), 3.91-3.83 (m, 1H), 2.91-2.79 (m, 2H), 2.45 (s, 3H), 1.39
(t, J = 7.1 Hz, 3H), 1.02 (t, J= 7.1 Hz, 3H);The carbon-13 nmr spectra of compound is as follows:13C
NMR (100 MHz, CDCl3) δ 171.7, 167.0, 164.9, 145.3, 135.2, 134.6, 134.0,
129.9, 129.7, 129.0, 128.7, 77.2, 63.3, 62.7, 46.1, 36.3, 21.7, 13.9, 13.5;
The Low Resolution Mass Spectra data of compound are as follows: MS (ESI) calcd for C23H25ClNO7S (M+H)+: 494.1,
found: 494.1;The high resolution mass spectrum data of compound is as follows: HRMS (ESI) calcd for C23H25ClNO7S (M+
H)+: 494.1035, found 494.1034。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (1)
1. a kind of method that N-heterocyclic carbine catalyzes and synthesizes polysubstituted pyrrole alkane ketone compounds, it is characterised in that:
Preparation method are as follows: under nitrogen protection, 0.05 mmol α-aminoacidesters are sequentially added into a dry reaction pipe,
0.01 mmolNHC , 0.1 mmolK2CO3 , 0.075 mmol oxidant, then 0.075 mmol olefine aldehydr is added into system
5 mL CH3CN, reacting 12 h at room temperature terminates, and stops stirring；Column chromatography, eluent: ethyl acetate and petroleum ether are with volume ratio
1:3 mixing, collects component, and obtaining corresponding product is yellow solid, yield 75%, the title of product are as follows: 5- oxo -3- phenyl -1- first
Benzenesulfonyl pyrrolidines -2,2- diethyl dicarboxylate, structural formula are as follows:
,
Wherein oxidant is 1,4-benzoquinone, reaction equation are as follows:
；
Or under nitrogen protection, 0.5 mmol α-aminoacidesters are sequentially added into a dry reaction pipe, 0.075
mmolNHC, 0.75 mmolK2CO3, then 50 mL are added to 1 mmol methyl cinnamic aldehyde in 1 mmol oxidant into system
CH3CN, reacting 12 h at room temperature terminates, and stops stirring；Column chromatography, eluent: ethyl acetate and petroleum ether are mixed with volume ratio 1:3
Close, collect component, obtaining corresponding product is white solid, yield 82%, the title of product are as follows: 5- oxo -3-(p-methylphenyl) -1-
Tosyl pyrrolidines -2,2- diethyl dicarboxylate, structural formula are as follows:
, wherein oxidant is manganese dioxide, reaction equation are as follows:
；
Or under nitrogen protection, 0.2 mmol α-aminoacidesters are sequentially added into a dry reaction pipe, 0.02 mmolNHC,
0.6 mmolEt325 mL CH are added to chlorocinnamaldehyde, then into system by N, 0.2 mmol2Cl2, anti-at room temperature in air
It answers 15 h to terminate, stops stirring；Solvent is evaporated, using CH2Cl2With n-hexane recrystallize corresponding product is white solid, yield
81%, the title of product are as follows: 3-(4- chlorphenyl) -5- oxo -1- tosyl pyrrolidines -2,2- diethyl dicarboxylate；Structure
Formula is as follows:
, wherein oxidant is air, reaction equation are as follows:
。
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| CN101066945A (en) * | 2007-05-25 | 2007-11-07 | 中国科学院上海有机化学研究所 | Process of synthesizing 3-substituted lactan compound |
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| CN101066945A (en) * | 2007-05-25 | 2007-11-07 | 中国科学院上海有机化学研究所 | Process of synthesizing 3-substituted lactan compound |
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| Design and synthesis of 3-arylpyrrolidine-2-carboxamide derivatives as melanocortin-4 receptor ligands;Joe A. Tran，等;《Bioorganic & Medicinal Chemistry Letters》;20080207;第18卷;第1931-1938页 |
| Highly Diastereo- and Enantioselective Additions of Homoenolates to Nitrones Catalyzed by N-Heterocyclic Carbenes;Eric M. Phillips，等;《Journal of the American Chemical Society》;20081231;第130卷;第2416-2417页 |
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| N-Heterocyclic Carbene Catalyzed Cyclocondensation of α,β-Unsaturated Carboxylic Acids: Enantioselective Synthesis of Pyrrolidinone and Dihydropyridinone Derivatives;Xiang-Yu Chen，等;《Angew. Chem. Int. Ed.》;20141231;第53卷(第43期);第11611-11615页 |
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